JPH0151A - Process for producing tetrakis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane - Google Patents
Process for producing tetrakis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyloxymethyl]methaneInfo
- Publication number
- JPH0151A JPH0151A JP63-21626A JP2162688A JPH0151A JP H0151 A JPH0151 A JP H0151A JP 2162688 A JP2162688 A JP 2162688A JP H0151 A JPH0151 A JP H0151A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- pentaerythritol
- hydroxyphenyl
- butyl
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title description 17
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 title 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000005809 transesterification reaction Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 5
- 239000007983 Tris buffer Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 34
- 229940059574 pentaerithrityl Drugs 0.000 description 29
- 239000006227 byproduct Substances 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000001953 recrystallisation Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- -1 that is Chemical compound 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
(産業上の利用分野〕
本発明は、ポリオレフィンなどの酸化防止剤として賞月
されているテトラキス(3−(3,5−ジ第3級ブチル
−4−ヒドロキシフェニル)プロピオニルオキシメチル
コメタン〔以下、化合物(1)と略することもある〕の
製造法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to the use of tetrakis (3-(3,5-ditertiary butyl-4-hydroxyphenyl)), which has been praised as an antioxidant for polyolefins and the like. This invention relates to a method for producing propionyloxymethylcomethane (hereinafter sometimes abbreviated as compound (1)).
化合物(1)はペンタエリスリトールと、少なくともペ
ンタエリスリトールに対して化学量論量以上の、すなわ
ち、少なくともペンタエリスリトール1モルに対して4
モル以上の3−(3,5−ジ第3級ブチル−4−ヒドロ
キシフェニル)プロピオン酸アルキルエステル〔以下、
化合物(II)と略することもある〕とを、たとえばア
ルカリ金属低級アルコキシドなどの触媒の存在下にエス
テル交換反応を行なうことにより製造し得ることは公知
である(特公昭42−19083号公報明細書)。Compound (1) contains pentaerythritol in at least a stoichiometric amount with respect to pentaerythritol, that is, at least 4 with respect to 1 mole of pentaerythritol.
3-(3,5-ditertiary-butyl-4-hydroxyphenyl)propionic acid alkyl ester [hereinafter referred to as
It is known that compound (II) (sometimes abbreviated as compound (II)) can be produced by transesterification in the presence of a catalyst such as an alkali metal lower alkoxide (Japanese Patent Publication No. 19083/1983). book).
この方法により、化合物(1)を製造する際に前記公報
明細書に記載されるように、不純物として、特にペンタ
エリスリトールの水酸基が置換不完了の生成物、すなわ
ち式
で表わされるペンタエリスリトールのトリ置換物〔以下
、副生物と略することもある〕が副生し混入する。As described in the specification of the above-mentioned publication, when producing compound (1) by this method, as an impurity, especially a product in which the hydroxyl group of pentaerythritol is incompletely substituted, that is, a trisubstituted pentaerythritol represented by the formula Substances (hereinafter sometimes abbreviated as by-products) are produced as by-products and mixed in.
この副生物(III)の副生は、当然のことながら目的
とする化 合物(1)の収率を低下させる。さらに、本
発明者らの知見に よれば副生物(I[[)は単なる再
結晶法によっては、化合物(I)との分離が困難であり
、化合物(1)の純度を向上できなかった。したがって
、副生物(III)の生成を抑制させることは工業上極
めて好ましいことである。This by-product (III) naturally reduces the yield of the target compound (1). Furthermore, according to the findings of the present inventors, it was difficult to separate the by-product (I[[) from compound (I) by a simple recrystallization method, and the purity of compound (1) could not be improved. Therefore, it is industrially extremely desirable to suppress the production of by-product (III).
一方、当該公報明細書では化合物(It)を化学量論量
より最大15%までの過剰量、すなわち、ペンタエリス
リトール1モルに対して、該化合物(n)を最大4.6
モルまで使用して副生物(III)の生成を抑制する旨
の示唆が記載されている0本発明者らは、この示唆に基
づき化合物(If)とペンタエリスリトールとのモル比
と副生物(I[)生成量との関係を詳細に調べたところ
、ペンタエリスリトール1モルに対して化合物(II)
を4.6モル以上使用すれば、副生物(III)の生成
量をペンタエリスリトールを基準として約10%、好ま
しくは約5%以下の収率に抑制でき、その後の精製工程
を終えることにより、実質的に副生物(III)の存在
しない目的物(1)が得られることを知ったが、この方
法では高価な化合物(■)を未反応のままに損失せざる
を得なく、製品コストが高いものであった。On the other hand, in the specification of the publication, the compound (It) is added in an excess amount of up to 15% over the stoichiometric amount, that is, the compound (n) is added in an amount of up to 4.6% with respect to 1 mole of pentaerythritol.
Based on this suggestion, the present inventors determined the molar ratio of compound (If) and pentaerythritol and the by-product (I). [) A detailed investigation of the relationship with the production amount revealed that compound (II) per mole of pentaerythritol
If 4.6 mol or more of is used, the amount of by-product (III) produced can be suppressed to a yield of about 10%, preferably about 5% or less based on pentaerythritol, and by completing the subsequent purification step, I learned that it is possible to obtain the target product (1) with virtually no by-product (III), but this method has no choice but to lose the expensive compound (■) unreacted, which increases the product cost. It was expensive.
(課題を解決するための手段)
以上の課題を解決すべく本発明者らは、原料として化合
物(II)とペンタエリスリトールとを使用して、化合
物(1)を製造する際に高価な化合物(II)を多量に
使用することなく、副生物(I[)の生成量を少量とし
て、収率よく純度の高い化合物N)を製造する方法を提
供することを目的として、鋭意研究を重ねた結果、本発
明を完成させるに至った。(Means for Solving the Problems) In order to solve the above problems, the present inventors used compound (II) and pentaerythritol as raw materials to produce compound (1). The result of extensive research aimed at providing a method for producing compound N) with high yield and high purity without using large amounts of II) and with a small amount of by-product (I[) produced. , we have completed the present invention.
すなわち、本発明者らは化合物(It)とペンタエリス
リトールとをエステル交換反応させる際、式で表わされ
るビス(2,2,2−トリス(ヒドロキシメチル)エト
キシコメタン(ペンタエリスリトールのビス体と略する
こともある)をペンタエリスリトールに対して、好まし
くは少量、就中0.05〜1.5重量%反応系に共存さ
せると、副生物(rl)の生成を少量とすることができ
、しかも、収率よく目的物(1)を得ることができると
いう驚くべき事実を見出した。That is, when the present inventors carried out a transesterification reaction between compound (It) and pentaerythritol, the present inventors obtained bis(2,2,2-tris(hydroxymethyl)ethoxycomethane) (abbreviated as the bis form of pentaerythritol) represented by the formula. By coexisting in the reaction system preferably a small amount, especially 0.05 to 1.5% by weight of pentaerythritol, the production of by-products (rl) can be reduced to a small amount. We have discovered the surprising fact that the target product (1) can be obtained in good yield.
したがって、本発明は塩基性触媒の存在下、化合物(I
I)とペンタエリスリトールとをエステル交換反応させ
るに際し、ビス(2,2,2−)リス(ヒドロキシメチ
ル)エトキシコメタンの存在下に反応を行なうことを特
徴とするテトラキス(3−(3゜5−ジ第3級ブチル−
4−ヒドロキシフェニル)プロピオニルオキシメチルコ
メタンの製造法に関する。Therefore, the present invention provides compound (I) in the presence of a basic catalyst.
Tetrakis(3-(3°5 -di-tertiary butyl-
The present invention relates to a method for producing 4-hydroxyphenyl)propionyloxymethylcomethane.
本発明の方法に従えば、高価な化合物(II)の使用量
がペンタエリスリトール1モルに対して、4.2〜4.
4モルとわずかな過剰量であっても、副生物(■)の生
成量をペンタエリスリトール基準で収率約10%以下、
好ましくは約5%以下とすることができ、しかも収率よ
く化合物(1)を得ることができ、単純な再結晶法によ
る精製を適用するだけで高純度の化合物(1)を得るこ
とができる。なお、化合物(II)とペンタエリスリト
ールのビス体とは、一部属応し、ペンタエリスリトール
のビス体のジまたはトリ置換体が副生ずるが、その量は
わずかであるので、化合物(n)の損失は少な(、また
再結晶法により当該副生物を容易に除去できるので化合
物(1)の純度を下げることはない。According to the method of the present invention, the amount of expensive compound (II) used is 4.2 to 4.5% per mole of pentaerythritol.
Even if there is a slight excess of 4 moles, the yield of the by-product (■) will be approximately 10% or less based on pentaerythritol.
It is preferably about 5% or less, and compound (1) can be obtained in good yield, and highly pure compound (1) can be obtained by simply applying purification by a simple recrystallization method. . Note that Compound (II) and the bis form of pentaerythritol are partially related, and di- or tri-substituted forms of the bis form of pentaerythritol are produced as by-products, but the amount is small, so there is no loss of compound (n). (Also, since the by-products can be easily removed by recrystallization, the purity of compound (1) is not reduced.
以下、本発明を詳述するが、これにより本発明の構成、
利点がよりよく理解されるであろう。Hereinafter, the present invention will be explained in detail, and the structure of the present invention,
The benefits will be better understood.
本発明では、化合物(II)のアルキルエステルとして
は、特に炭素数1〜4のアルキルエステル、具体的には
メチルエステルまたはエチルエステルが好ましい。In the present invention, the alkyl ester of compound (II) is particularly preferably an alkyl ester having 1 to 4 carbon atoms, specifically a methyl ester or an ethyl ester.
化合物(n)は、ペンタエリスリトールに対して化学量
論量よりやや過剰、すなわち、ペンタエリスリトール1
モル部に対して、約4.2〜4.4モル部使用すること
が好ましいが、それ以上使用してもよい。Compound (n) is present in a slightly excess stoichiometric amount relative to pentaerythritol, that is, pentaerythritol 1
It is preferable to use about 4.2 to 4.4 parts by mole based on the mole part, but more than that may be used.
従来法では、この程度の過剰量では、前記副生物(■)
が相当量生成し、再結晶によっても除去されないので、
目的物(I)の純度が低かうたが、本発明の方法では副
生物(III)の副生量が少なく、後記する単純な再結
晶法により除去できるので、高純度の製品として化合物
(1)が得られる。In the conventional method, in such an excessive amount, the above-mentioned by-product (■)
is produced in considerable amounts and is not removed even by recrystallization,
Although it is said that the purity of the target compound (I) is low, in the method of the present invention, the amount of the by-product (III) is small and it can be removed by the simple recrystallization method described later. ) is obtained.
本発明の方法にあっては、エステル交換反応触媒を使用
する。その塩基性触媒としては、従来公知の触媒が使用
できる。具体的には、水素化ナトリウム、水素化カルシ
ウム、水素化リチウムなどのアルカリ金属またはアルカ
リ土類金属の水素化物;リチウムメトキシド、ナトリウ
ムメトキシド、カリウムメトキシド、リチウムエトキシ
ド、ナトリウム第3級ブトキシド、カリウム第3級ブト
キシドなどのアルカリ金属低級アルコキシド;金属ナト
リウム、金属カリウムなどのアルカリ金属;ジブチル錫
オキシド、モノブチル錫オキシド、トリブチル錫オキシ
ドなどの有機錫酸化物などを例示できるが、なかでも有
機錫酸化物の使用が好ましい、このような触媒は、従来
公知の量を使用すれば充分であり、通常、化合物(II
)100重量部に対して0.1〜10重量部、好まし、
くは0.3〜3重量部使用する。また、本発明のエステ
ル交換反応においては、溶媒を使用することが好ましい
、使用される溶媒としてはジメチルスルホキシド、ジメ
チルホルムアミド、テトラヒドロフラン、ジオキサン、
ジグライム、ジメチルアセトアミド、ヘキサメチルホス
ホアミド、1.2−ジメトキシエタン、アセトニトリル
、第3級ブタノール、トルエン、キシレン、ヘキサン、
ヘプタンなどを例示することができるが、なかでもトル
エン、キシレンの使用が好ましい、溶媒は、化合物(■
)1重量部に対して最大5重量部使用され、好ましくは
0.1〜10重量部使用される。In the method of the present invention, a transesterification catalyst is used. As the basic catalyst, conventionally known catalysts can be used. Specifically, hydrides of alkali metals or alkaline earth metals such as sodium hydride, calcium hydride, and lithium hydride; lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, and sodium tertiary butoxide. , alkali metal lower alkoxides such as potassium tert-butoxide; alkali metals such as metallic sodium and metallic potassium; organotin oxides such as dibutyltin oxide, monobutyltin oxide, and tributyltin oxide; It is sufficient to use conventionally known amounts of such catalysts, the use of which is preferably oxides, and usually the compound (II
) 0.1 to 10 parts by weight per 100 parts by weight, preferably
0.3 to 3 parts by weight is used. Further, in the transesterification reaction of the present invention, it is preferable to use a solvent. Examples of the solvent used include dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane,
diglyme, dimethylacetamide, hexamethylphosphoamide, 1,2-dimethoxyethane, acetonitrile, tertiary butanol, toluene, xylene, hexane,
Examples of solvents include heptane, among others, toluene and xylene are preferable.
) is used in a maximum of 5 parts by weight, preferably 0.1 to 10 parts by weight.
本発明において最も重要な要件は、エステル交換反応時
にペンタエリスリトールのビス体を反応系内に存在させ
ることであり、かつ、その量をペンタエリスリトールに
対して、好ましくは0.05〜1.5重量%とすること
である。このような手段を採用することにより、前記副
生物(III)の副生量をペンタエリスリトール基準で
約lO%、好ましく約5%以下の収率とすることが可能
となる。ペンタエリスリトールのビス体の量が0.05
重量%未満では副生物(I)の生成量が多く、1.5重
量%を越えるとペンタ ・エリスリトールのビス体と化
合物(II)との反応が無視できない程進行し、高価な
化合物(II)を無駄に損失するとともに、後記する精
製工程で目的物(I)の再結晶率が著しく低下するなど
の欠点を有する。The most important requirement in the present invention is that the bis form of pentaerythritol is present in the reaction system during the transesterification reaction, and the amount thereof is preferably 0.05 to 1.5% by weight relative to pentaerythritol. %. By employing such means, it is possible to reduce the amount of the by-product (III) to a yield of about 10%, preferably about 5% or less, based on pentaerythritol. The amount of bis form of pentaerythritol is 0.05
If it is less than 1.5% by weight, a large amount of by-product (I) will be produced, and if it exceeds 1.5% by weight, the reaction between the bis form of penta-erythritol and compound (II) will proceed to a non-negligible level, resulting in the production of expensive compound (II). This method has drawbacks such as a wasteful loss of the target substance (I) and a marked decrease in the recrystallization rate of the target product (I) in the purification process described later.
本発明のエステル交換反応は、実質的にメタノール、エ
タノールなどのアルコールの生成が終了するまで行なわ
れ、通常80〜200℃の温度で5〜20時間実施され
る。該生成アルコールは反応系から除去される。除去方
法は、エステル交換反応を行なう際の通常の手段が採用
され、たとえば5〜50mmHgの減圧下で留出させる
方法などがあげられる。The transesterification reaction of the present invention is carried out until substantially the production of alcohols such as methanol and ethanol is completed, and is usually carried out at a temperature of 80 to 200°C for 5 to 20 hours. The produced alcohol is removed from the reaction system. For the removal method, a usual means for carrying out transesterification reaction is employed, such as a method of distilling under reduced pressure of 5 to 50 mmHg.
その際、特別な装置は必要とせず撹拌装置、加熱装置、
上記アルコールの留出装置を付した反応容器であれば、
いずれも使用できる。At that time, no special equipment is required; stirring equipment, heating equipment,
If it is a reaction vessel equipped with the above-mentioned alcohol distillation device,
Either can be used.
次に、エステル交換反応終了後の反応生成物から化合物
(1)が精製分離される。この精製分離手段としては、
好ましくは再結晶法が採用される。このとき使用される
溶媒としては、ヘキサン、シクロヘキサン、ヘプタン、
メタノール、エタノール、プロパツール、イソプロパツ
ール、ブタノール、イソブタノールなどを例示できるが
、好ましくはメタノールまたはエタノールが使用される
。再結晶法に使用される溶媒は純粋である必要はなく、
たとえば市販のエタノールは約5%の水分を含有してい
るが、これでも充分使用可能である。Next, compound (1) is purified and separated from the reaction product after completion of the transesterification reaction. As this purification and separation means,
Preferably, a recrystallization method is employed. Solvents used at this time include hexane, cyclohexane, heptane,
Examples include methanol, ethanol, propatool, isopropanol, butanol, isobutanol, and preferably methanol or ethanol is used. The solvent used in the recrystallization method does not need to be pure;
For example, commercially available ethanol contains about 5% water, which is still usable.
この再結晶法による精製分離操作では、前記反応生成物
中に化合物(1)が高収率で存在し、しかも副生物が少
ないので損失が少ない。In the purification and separation operation using this recrystallization method, compound (1) is present in the reaction product in high yield, and there are few by-products, so there is little loss.
以上、詳述した本発明の方法により製造される化合物(
1)は、前記副反応物(Ill)などの副生物の含量が
少なく高純度であり、たとえば酸化防止剤として優れて
いる。The compounds produced by the method of the present invention detailed above (
1) has a low content of by-products such as the above-mentioned by-product (Ill), has high purity, and is excellent as an antioxidant, for example.
以下、具体的に実施例にまり本発明を説明するが、本発
明はこれにより限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.
実施例!
撹拌機、還流冷却器、温度計および窒素導入管を備えた
lj!容40フラスコにトルエン300 g、ジブチル
錫オキシドλOg、ペンタエリスリトール44.2g、
純度99%以上の3−(3,5−ジ第3級ブチル−4−
ヒドロキシフェニル)プロピオン酸メチル420 g、
ビス(2,2,2−トリス(ヒドロキシメチル)エトキ
シコメタン0.11 gを加え、170〜175°Cで
12時間加熱撹拌しながら、生成するメタノールおよび
トルエンを留去した0反応終了後、トルエン300g、
シュウ酸2.0gおよびツルカフロック12gを加え、
還流下に脱水した。Example! lj! equipped with stirrer, reflux condenser, thermometer and nitrogen inlet tube! In a 40-volume flask, 300 g of toluene, λOg of dibutyltin oxide, 44.2 g of pentaerythritol,
3-(3,5-di-tert-butyl-4- with a purity of 99% or more)
420 g of methyl hydroxyphenyl)propionate,
After adding 0.11 g of bis(2,2,2-tris(hydroxymethyl)ethoxycomethane) and distilling off the methanol and toluene produced while stirring at 170 to 175°C for 12 hours, 300g toluene,
Add 2.0 g of oxalic acid and 12 g of Tulka floc,
Dehydrated under reflux.
トルエンに不溶のジブチル錫オキシドのシュウ酸塩およ
びツルカフロックを濾過して除き、次いでトルエンを減
圧下に留去したところ、淡黄色飴状物質420gを得た
。この飴状物質を分析した結果、テトラキス(3−(3
,5−ジ第3級ブチル−4−ヒドロキシフェニル)プロ
ピオニルオキシメチルコメタンがペンタエリスリトール
基準で、理論収率97.0%で生成していることおよび
副生物がペンタエリスリトール基準で、理論収率2.8
%で生成していることが認められた。The oxalate of dibutyltin oxide insoluble in toluene and Tulka floc were removed by filtration, and the toluene was then distilled off under reduced pressure to obtain 420 g of a pale yellow candy-like substance. As a result of analyzing this candy-like substance, we found that tetrakis (3-(3
, 5-ditert-butyl-4-hydroxyphenyl)propionyloxymethyl comethane is produced at a theoretical yield of 97.0% based on pentaerythritol, and the by-product is produced at a theoretical yield of 97.0% based on pentaerythritol. 2.8
% was observed.
続いて、飴状物質を95%メタノール−水で再結晶する
と、白色結晶として97%の得率で目的物を得た。この
結晶の純度は99%以上であり、前記副生物の含量は1
重量%以下であった。Subsequently, the candy-like substance was recrystallized from 95% methanol-water to obtain the desired product as white crystals with a yield of 97%. The purity of this crystal is over 99%, and the content of the by-products is 1.
It was less than % by weight.
実施例2〜4
実施例1において、ビス(2,2,2−)リス(ヒドロ
キシメチル)エトキシコメタンの使用量をペンタエリス
リトールに対して各々0.5重量%(実施例2)、0.
05重量%(実施例3)、1.5重量%(実施例4)と
する以外は、実施例1と同一の操作を行なった。Examples 2 to 4 In Example 1, the amount of bis(2,2,2-)lis(hydroxymethyl)ethoxycomethane used was 0.5% by weight relative to pentaerythritol (Example 2), and 0.5% by weight, respectively, based on pentaerythritol.
The same operation as in Example 1 was performed except that the amounts were 0.05% by weight (Example 3) and 1.5% by weight (Example 4).
化合物(1)の収率、得率、副生物の収率および純度に
関する結果を、実施例1とあわせて第1表に示した。The results regarding the yield and yield of compound (1), the yield of by-products, and the purity are shown in Table 1 together with Example 1.
なお、実施例3.4で得られた結晶をイソプロパツール
を用いて再度再結晶を行なったが純度は第1表に示され
た値と同一であった。The crystals obtained in Example 3.4 were recrystallized again using isopropanol, and the purity was the same as the value shown in Table 1.
第 1 表
〔発明の効果〕
本発明方法によると、目的とするテトラキス[3−(3
,5−ジ第3級ブチル−4−ヒドロキシフェニル)プロ
ピオニルオキシメチルコメタンが高収率、かつ高純度に
製造される。Table 1 [Effects of the invention] According to the method of the present invention, the desired tetrakis[3-(3
, 5-ditert-butyl-4-hydroxyphenyl)propionyloxymethylcomethane is produced in high yield and with high purity.
Claims (1)
−4−ヒドロキシフェニル)プロピオン酸アルキルエス
テルとペンタエリスリトールをエステル交換反応させる
に際し、ビス〔2,2,2−トリス(ヒドロキシメチル
)エトキシ〕メタンの存在下に反応を行なうことを特徴
とするテトラキス〔3−(3,5−ジ第3級ブチル−4
−ヒドロキシフェニル)プロピオニルオキシメチル〕メ
タンの製造法。[Scope of Claims] In the transesterification reaction of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid alkyl ester and pentaerythritol in the presence of a basic catalyst, bis[2, Tetrakis[3-(3,5-di-tert-butyl-4) characterized by carrying out the reaction in the presence of 2,2-tris(hydroxymethyl)ethoxy]methane.
-Hydroxyphenyl)propionyloxymethyl]methane production method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63021626A JPH0751536B2 (en) | 1987-02-03 | 1988-02-01 | Process for producing tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2416387 | 1987-02-03 | ||
JP62-24163 | 1987-02-03 | ||
JP63021626A JPH0751536B2 (en) | 1987-02-03 | 1988-02-01 | Process for producing tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane |
Publications (3)
Publication Number | Publication Date |
---|---|
JPS6451A JPS6451A (en) | 1989-01-05 |
JPH0151A true JPH0151A (en) | 1989-01-05 |
JPH0751536B2 JPH0751536B2 (en) | 1995-06-05 |
Family
ID=12130672
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63021626A Expired - Lifetime JPH0751536B2 (en) | 1987-02-03 | 1988-02-01 | Process for producing tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane |
Country Status (5)
Country | Link |
---|---|
US (1) | US4883902A (en) |
EP (1) | EP0300056B1 (en) |
JP (1) | JPH0751536B2 (en) |
DE (1) | DE3868164D1 (en) |
WO (1) | WO1988005773A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH085844B2 (en) * | 1989-06-08 | 1996-01-24 | 吉富製薬株式会社 | ALPHA.-Crystal tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane having excellent fluidity and method for producing the same |
US5136082A (en) * | 1990-08-03 | 1992-08-04 | Himont Incorporated | Process for preparing organic esters and amides and catalyst system therefor |
TW289752B (en) * | 1994-03-11 | 1996-11-01 | Ciba Geigy Ag | |
GB0324964D0 (en) * | 2003-10-27 | 2003-11-26 | Great Lakes Chemical Europ | Preparation of hydroxyphenyl carboxylic acid esters |
US9567284B2 (en) * | 2012-10-24 | 2017-02-14 | Kh Neochem Co., Ltd. | Hexaester of mono-formal bis pentaerythritol |
US9365484B2 (en) * | 2012-10-24 | 2016-06-14 | Kh Neochem Co., Ltd. | Hexaester of mono-formal bis pentaerythritol |
CN104230705A (en) * | 2013-06-08 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method for pentaerythritol tetracarboxylate |
JP6888324B2 (en) * | 2017-02-23 | 2021-06-16 | 株式会社村田製作所 | Manufacturing method of multilayer ceramic electronic components |
JP7109697B1 (en) * | 2022-04-27 | 2022-07-29 | 株式会社Adeka | Method for producing tetrakis[methylene-3-(3',5'-tert-butyl-4'-hydroxyphenyl)propionate]methane |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3779945A (en) * | 1961-10-30 | 1973-12-18 | Geigy Ag J R | Mixtures of 3-(3,5-dialkyl-4-hydroxyphenyl)-propionic acid esters of alkanediols |
US4396552A (en) * | 1980-02-08 | 1983-08-02 | Ciba-Geigy Corporation | Novel metal mercaptides of esters of β-mercaptoalkanols |
JPS57197245A (en) * | 1981-05-28 | 1982-12-03 | Mitsui Petrochem Ind Ltd | Tetrakis(3-(3,5-dibutyl-4-hydroxyphenyl) propionyloxymethyl)methane |
US4511491A (en) * | 1982-07-26 | 1985-04-16 | Sumitomo Chemical Co., Ltd. | Stabilizers for synthetic resins |
US4594444A (en) * | 1983-12-22 | 1986-06-10 | Ciba-Geigy Corporation | Process for the preparation of sterically hindered hydroxyphenylcarboxylic acid esters |
US4716244A (en) * | 1985-05-02 | 1987-12-29 | Ciba-Geigy Corporation | Process for the preparation of sterically hindered hydroxyphenylcarboxylic acid esters |
US4683326A (en) * | 1985-07-19 | 1987-07-28 | Ciba-Geigy Corporation | Solvent-free crystallization of pentaerythritol tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and the novel alpha-crystalline form thereof |
KR910003810B1 (en) * | 1988-12-31 | 1991-06-12 | 삼성전관 주식회사 | Structure of pdp and driving method of the same |
JP3633673B2 (en) * | 1995-07-11 | 2005-03-30 | 三菱瓦斯化学株式会社 | Prepreg and laminate |
-
1988
- 1988-02-01 DE DE8888901318T patent/DE3868164D1/en not_active Expired - Fee Related
- 1988-02-01 US US07/275,175 patent/US4883902A/en not_active Expired - Fee Related
- 1988-02-01 WO PCT/JP1988/000088 patent/WO1988005773A1/en active IP Right Grant
- 1988-02-01 EP EP88901318A patent/EP0300056B1/en not_active Expired
- 1988-02-01 JP JP63021626A patent/JPH0751536B2/en not_active Expired - Lifetime
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2818640B2 (en) | Process for producing alkyl imidazolidone (meth) acrylate | |
EP0066189A1 (en) | A process for preparing tetrakis (3-(3,5-dibutyl-4-hydroxyphenyl)propionyloxymethyl)methane | |
JPH0151A (en) | Process for producing tetrakis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane | |
US4694099A (en) | Procedure for producing stearyl-β-(3,5-dibutyl-4-hydroxyphenyl) propionate and bis-(β(3,5-dibutyl-4-hydroxybenzyl)-methylcarboxyethyl)sulphide | |
JPH0751536B2 (en) | Process for producing tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) propionyloxymethyl] methane | |
US4618700A (en) | Process for the preparation of a hydroxyphenylcarboxylate | |
US4885382A (en) | Method of producing tetrakis[3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane | |
JPH1053561A (en) | Production of 2-oxocarboxylic acid ester | |
JPH0710811A (en) | Production of dialkyl carbonate | |
JPS6013015B2 (en) | Method for producing tetrakis[3-(3,5-dibutyl-4-hydroxyphenyl)propionyloxymethyl]methane | |
JPH0142254B2 (en) | ||
JPH01265058A (en) | Production of tetrakis(3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propionyloxymethyl)methane | |
KR100542820B1 (en) | Method of Preparing 1-Ethyl-2,3-Dioxopiperazine using oxalyl chloride | |
JP2976245B2 (en) | Method for producing hydroxyphenylpropionate | |
JPH0142253B2 (en) | ||
JPH0648988A (en) | Production of tetrakis(3-@(3754/24)3,5-dialkyl-4--hydroxyphenyl) propionyloxyalkyl) methane | |
JP3311372B2 (en) | Method for producing 3-N, N-dialkylaminophenol derivative | |
JP4004640B2 (en) | α- (Alkoxyoxalyl) fatty acid ester and α-alkyl or alkenyl acrylate ester, and method for synthesizing phenylidone using the same | |
JP4030289B2 (en) | Process for producing β-ketonitriles | |
JPH0321537B2 (en) | ||
JP3474009B2 (en) | Method for producing ester compound effective as electron donating compound for Ziegler-Natta catalyst | |
JP3240205B2 (en) | Method for producing 2-alkoxycarbonylmethylcarbonylpyrazine | |
JPH0353298B2 (en) | ||
SU1205756A3 (en) | Method of producing 1,1-dichlor-4-methylpentadiens | |
US5101043A (en) | Process for the preparation of 3-carboxamido-5-vinyl-2-pyrrolidone |